Clinical diagnosis has always been dependent on the efficient immobilization of biomolecules in solid matrices with preserved activity, but significant developments have taken place in recent years with the increasing control of molecular architecture in organized films. Of particular importance is the synergy achieved with distinct materials such as nanoparticles, antibodies, enzymes, and other nanostructures, forming structures organized on the nanoscale. In this review, emphasis will be placed on nanomaterials for biosensing based on molecular recognition, where the recognition element may be an enzyme, DNA, RNA, catalytic antibody, aptamer, and labeled biomolecule. All of these elements may be assembled in nanostructured films, whose layer-by-layer nature is essential for combining different properties in the same device. Sensing can be done with a number of optical, electrical, and electrochemical methods, which may also rely on nanostructures for enhanced performance, as is the case of reporting nanoparticles in bioelectronics devices. The successful design of such devices requires investigation of interface properties of functionalized surfaces, for which a variety of experimental and theoretical methods have been used. Because diagnosis involves the acquisition of large amounts of data, statistical and computational methods are now in widespread use, and one may envisage an integrated expert system where information from different sources may be mined to generate the diagnostics.
In the last decade, several studies from different fields have contributed significantly to the development of the enzyme biofuel cell (BFC). Moreover, the design of biocatalyst‐modified electrodes is a model for the development of synthetic and biomimetic electrocatalysts. The revival of the interest in the old BFC idea developed in the early 20th century is related to the development of new electrode materials as well as to the potential application of enzyme BFC miniaturisation in implantable bioelectronics. Furthermore, fundamental studies on half‐cells and electron transfer involving protein film electrodes performed in the last few decades have established new types of electrodes for BFC applications. In terms of applicability, some research groups have sought to obtain unit cells with different properties and characteristics such as membrane‐less BFCs by using flexible and low‐costing materials; in addition, micrometric BFCs, which can be implanted in different body parts, have also been developed to supply electrical power to bioelectronics devices. Thus, in this review, we focus on introducing the main concepts and challenges in enzyme BFC research. Some important topics in kinetics and thermodynamics applied to BFCs are also discussed. Wherever possible, an extensive review of works undertaken in recent years is performed. The topics are organised into three major themes: thermodynamics, kinetics and challenges in applicability.
In this work, we exploit the molecular engineering capability of the layer-by-layer (LbL) method to immobilize layers of gold nanoparticles on indium tin oxide (ITO) substrates, which exhibit enhanced charge transfer and may incorporate mediating redox substances. Polyamidoamine (PAMAM generation 4) dendrimers were used as template/stabilizers for Au nanoparticle growth, with PAMAM-Au nanoparticles serving as cationic polyelectrolytes to produce LbL films with poly(vinylsulfonic acid) (PVS). The cyclic voltammetry (CV) of ITO-PVS/PAMAM-Au electrodes in sulfuric acid presented a redox pair attributed to Au surface oxide formation. The maximum kinetics adsorption is first-order, 95% of the current being achieved after only 5 min of adsorption. Electron hopping can be considered as the charge transport mechanism between the PVS/PAMAM-Au layers within the LbL films. This charge transport was faster than that for nonmodified electrodes, shown by employing hexacyanoferrate(III) as the surface reaction marker. Because the enhanced charge transport may be exploited in biosensors requiring redox mediators, we demonstrate the formation of Prussian blue (PB) around the Au nanoparticles as a proof of principle. PAMAM-Au@PB could be easily prepared by electrodeposition, following the ITO-PVS/ PAMAM-Au LbL film preparation procedure. Furthermore, the coverage of Au nanoparticles by PB may be controlled by monitoring the oxidation current.
Diagnosis of COVID-19 has been challenging owing to the need for
mass testing and for combining distinct types of detection to
cover the different stages of the infection. In this review, we
have surveyed the most used methodologies for diagnosis of
COVID-19, which can be basically categorized into
genetic-material detection and immunoassays. Detection of
genetic material with real-time polymerase chain reaction
(RT-PCR) and similar techniques has been achieved with high
accuracy, but these methods are expensive and require
time-consuming protocols which are not widely available,
especially in less developed countries. Immunoassays for
detecting a few antibodies, on the other hand, have been used
for rapid, less expensive tests, but their accuracy in
diagnosing infected individuals has been limited. We have
therefore discussed the strengths and limitations of all of
these methodologies, particularly in light of the required
combination of tests owing to the long incubation periods. We
identified the bottlenecks that prevented mass testing in many
countries, and proposed strategies for further action, which are
mostly associated with materials science and chemistry. Of
special relevance are the methodologies which can be integrated
into point-of-care (POC) devices and the use of artificial
intelligence that do not require products from a well-developed
biotech industry.
Electroactive nanostructured films of chitosan (Ch) and tetrasulfonated metallophthalocyanines containing nickel (NiTsPc), copper (CuTsPc), and iron (FeTsPc) were produced via the electrostatic layer-by-layer (LbL) technique. The multilayer formation was monitored with UV-vis spectroscopy by measuring the increase of the Q-band absorption from metallophthalocyanines. Results from transmission and reflection infrared spectroscopy suggested specific interactions between SO(3)(-) groups from metallophthalocyanines and NH(3)(+) from chitosan. The electroactive multilayered films assembled onto an ITO electrode were characterized by cyclic voltammetry, with Ch/NiTsPc films showing higher stability and well-defined voltammograms displaying reversible redox peaks at 0.80 and 0.75 V. These films could be used to detect dopamine (DA) in the concentration range from 5.0 x 10(-6) to 1.5 x 10(-4) mol L(-1). Also, ITO-(Ch/NiTsPc)(n)() electrodes showed higher electrocatalytic activity for DA oxidation when compared with a bare ITO electrode. On the other hand, only the Ch/FeTsPc and Ch/CuTsPc modified electrodes could distinguish between DA and ascorbic acid. These results demonstrate that versatile electrodes can be prepared by incorporation of different metallophthalocyanine molecules in LbL films, which may be used in bioanalytical applications.
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